Single crystal ESR study of x-irradiated thiophosphate O,O,O-triester of methyl β-D-ribopyranoside: Electron capture by the thiophosphate moiety

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Abstract
X‐irradiation of a single crystal of thiophosphate O,O,O‐triester of methyl β‐D‐ribopyranoside at 77 K produces a σ phosphoranyl radical anion (2) by electron capture among secondary radicals resulting from bond scission. The ESR parameters of (2) in correlation with the x‐ray analysis of its precursor establish a TBP structure with the unpaired electron in apical position. The results suggest that in irradiated nucleic acid polymers, electrons can be trapped by phosphorus giving rise to a phosphorus‐centered radical which subsequently induces bond break by α or β scission generating thermodynamically more stable sugar and base radicals.

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